JPH069842A - Plastisol - Google Patents

Abstract

PURPOSE:To obtain a plastisiol having excellent aging stability of viscosity and heat-meltability and giving a molded article having good volatilization resistance and freeze resistance by using a vinyl chloride paste resin and di-2- propylheptyl phthalate as main components. CONSTITUTION:The plastisol is produced by compounding (A) 100 pts.wt. of a vinyl chloride paste resin (a part of the resin may be substituted with a vinyl chloride blending resin having particle diameter of 10-40mum) with (B) 30-400 pts.wt. (preferably 50-200 pts.wt.) of di-2-propylheptyl phthalate and, as necessary, (C) plasticizers (e.g. dibutyl phthalate) and other additives.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastisol which is excellent in viscosity stability over time and heat-melting property and which can give a molded article having good volatility resistance and cold resistance.

[0002]

2. Description of the Related Art Conventionally, so-called plastisol, in which fine particles of plastic are uniformly dispersed in a plasticizer, has been widely used for molding sealing materials or underbody coating materials for automobiles, and for forming wallpaper, flooring materials, gloves and the like. There is. In the case of a sealing material and an underbody coating material for automobiles, plastisol is spray-coated on a substrate and then melted by heating. Also, for wallpaper, flooring, etc., by the spread coating method, boots,
In gloves and the like, the mold is dipped in plastisol to form a shape, and then heated and melted.

The plastisols used for these are vinyl chloride paste resin as a plastic and di-2-ethylhexyl phthalate (DOP) as a plasticizer.
However, it is widely used due to its balanced performance and price. However, when DOP is used as the plasticizer, the plastisol has poor viscosity stability, and the viscosity of plastisol increases over time, which makes it difficult to perform molding by the various molding methods. Further, in recent years, there has been a tendency to use a vinyl chloride / vinyl acetate copolymer for the purpose of improving the meltability at the time of heating and improving the physical properties of a molded product, and in using such a resin, DOP is more and more stable in viscosity. Tend to be inferior.

Plastisols are generally 140-200 ° C.
However, in the case of high temperature heating, there is a deterioration in quality due to volatilization of the plasticizer, and measures for the working environment are also required. Further, there is a problem that the plasticizer is gradually lost in the molded product as well over time, and the flexibility and strength, which are the features of the plastisol molded product, are reduced.

As a plasticizer for improving such drawbacks, diisononyl phthalate (DIN), which has a higher molecular weight than DOP and is expected to improve viscosity stability and volatility resistance, is used.
P), diisodecyl phthalate (DIDP), etc. are being studied. However, the problem has not been sufficiently improved even when using DINP and DIDP. That is, DINP has not yet achieved sufficient performance in terms of viscosity stability and volatility. Further, although DIDP is effective in improving the viscosity stability, it has a new problem that it has poor meltability and it is difficult to develop sufficient physical properties unless it is subjected to high temperature molding. Therefore, there is also a problem that flexibility at low temperatures is poor.

Therefore, the advent of plastisol, which has a good balance between viscosity stability and meltability, and has the low volatility and good cold resistance, has been awaited. Further, an invention of a vinyl chloride resin composition containing di-2-propylheptyl phthalate is disclosed in Japanese Patent Application Laid-Open No. 4-106146, but this invention is for wire coating, profile extrusion, and injection molding. The technical idea of the present invention of obtaining a plastisol which is a composition and has good viscosity stability and meltability is not included at all.

[0007]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention has been earnestly studied for the purpose of obtaining a molded article having excellent viscosity stability with time and melting property at low temperature and having good volatility resistance and cold resistance. As a plasticizer, di-2-phthalate
The inventors have found that the above object can be achieved by using propylheptyl, and have completed the present invention.

[0008]

The gist of the present invention is that a vinyl chloride paste resin and di-2-phthalic acid are used.
It is found in plastisols containing propylheptyl as the main component.
The present invention will be described in detail. The vinyl chloride paste resin, which is the resin component of the plastisol of the present invention, is obtained by emulsion-polymerizing vinyl chloride or a mixture of vinyl chloride or a comonomer copolymerizable therewith in an aqueous medium in the presence of a water-soluble polymerization catalyst, or by oil-soluble polymerization. It is produced by a method of fine suspension polymerization in the presence of a catalyst. This paste resin is usually less than 5μ,
It mainly has a particle size of 2 μ or less.

Examples of the comonomer copolymerizable with vinyl chloride include vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate, acrylic acid esters such as methyl acrylate and ethyl acrylate, and methacrylic acid. Methacrylic acid esters such as methyl acid and ethyl methacrylate, maleic acid esters such as dimethyl maleate and diethyl maleate, fumaric acid esters, vinyl ethers such as isobutyl vinyl ether and phenyl vinyl ether, acrylonitrile, styrene, vinylidene chloride, etc. Can be mentioned.

The plasticizer used in the plastisol of the present invention is a phthalic acid di-2-ester obtained by dehydration condensation esterification reaction of phthalic acid or phthalic anhydride and 2-propylheptanol in the presence of a catalyst by a method known per se. Propylheptyl. 2-propylheptanol is, for example,
It can be produced by converting butene-1 into n-valeraldehyde by an oxo reaction, and hydrogenating 2-propylheptenal obtained by aldol condensation of the n-valeraldehyde and dehydration reaction of the reaction product.

The plastisol of the present invention is obtained by uniformly mixing a vinyl chloride paste resin and di-2-propylheptyl phthalate. Vinyl chloride paste resin is
For the purpose of reducing the viscosity of the plastisol, a part thereof may be replaced with a so-called vinyl chloride cleansing resin having a particle size larger than that of the paste resin, for example, about 10 to 40 μm. The mixing ratio of the vinyl chloride paste resin (containing cleansing resin) and di-2-propylheptyl phthalate is appropriately selected depending on the desired solid content concentration of plastisol, fluidity, etc. 30 to 400 parts by weight, preferably 50 to 200 parts by weight.

Further, the plastisol of the present invention may be used in combination with other plasticizers within a range not impairing the effects of the present invention. The plasticizer that can be used in combination is not particularly limited as long as it is used for vinyl chloride resins,
For example, dibutyl phthalate (DBP), diheptyl phthalate (DHP), DOP, DINP, DIDP, diundecyl phthalate (DUP), phthalate ester such as butylbenzyl phthalate (BBP), di-2-ethylhexyl adipate (DOA), Diisononyl adipate (DINA), diisodecyl adipate (DID
Examples thereof include adipic acid esters such as A), phosphoric acid esters, and the like.

Further, various additives such as a filler, a stabilizer, a diluent, a thickener, a coloring agent and an adhesion-imparting agent can be added to the plastisol of the present invention, if necessary. Of course, other additives can be added as required. The plastisol of the present invention is prepared by uniformly mixing the vinyl chloride paste resin, di-2-propylheptyl phthalate and, if necessary, the above-mentioned various additives by a conventional method. Then, this plastisol is applied to an automobile and melted by heating, as an automobile sealing material or an underbody coating material,
Also, wallpaper that is heated and melted after being applied on the substrate by various methods,
It can be used as a resin raw material for flooring or the like, or as a resin raw material for immersion processing of boots, gloves and the like.

[0014]

EXAMPLES Next, the plastisol of the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. The test method for plastisol is as follows.

Viscosity of plastisol: After preparing plastisol, the viscosity at the time of standing at 40 ° C. for 3 hours and 3 days is B
Measured with a viscometer (unit: poise). Viscosity stability (AI): viscosity after 3 days / viscosity after 3 hours
Expressed as Physical property measurement: Plastisol was applied on a glass plate to a thickness of about 1 mm, and then 160 ° C. (Example 1 and Comparative Examples 1 and 2)
Alternatively, the mixture was heated and melted for 20 minutes in a dryer maintained at a temperature of 180 ° C. (Example 2 and Comparative Examples 3 and 4), taken out and cooled to obtain a test piece, and the following test method was applied to this test piece. Based on this, the test was conducted. Tensile test JIS K 7113 Volatilization loss ASTM D-1203-52T Low temperature flexible temperature ASTM D-1043-51

Synthesis of di-2-propylheptyl phthalate Tetraisopropoxy titanium (esterification catalyst) was prepared by adding a slight excess of 2-propylheptanol to phthalic anhydride.
In the presence of the above, an esterification reaction was carried out at a temperature of 200 ° C. according to a conventional method, and then excess 2-propylheptanol was distilled off, and dehydration filtration purification was performed to obtain di-2-propylheptyl phthalate.

Example 1, Comparative Example 1, 100 parts by weight of vinyl chloride paste resin (trade name Vinica P-500, manufactured by Mitsubishi Kasei Vinyl Co., Ltd.) was added to the above-mentioned di-2-propylheptyl phthalate, DINP and D
80 parts by weight of IDP was blended, uniformly stirred and mixed with a crusher, and then defoamed under vacuum to prepare a plastisol. The viscosity, viscosity stability and tensile test of these plastisols were tested and shown in Table 1.

[0018]

[Table 1]

Example 2, Comparative Examples 3 and 4 As in Example 1, except that the amount of the plasticizer used was 67 parts by weight and the stabilizer (Ba-Zn system) was added in an amount of 1 part by weight. A plastisol was prepared in the same manner.
Various physical properties of these plastisols were measured and are shown in Table 2.

[0020]

[Table 2]

As is clear from these Examples and Comparative Examples, the plastisol of the present invention has better viscosity stability and better volatility loss than the plastisol using DINP, and is comparable to the plastisol using DIDP. The viscosity stability is the same, but the low temperature melting property is excellent and the low temperature flexibility is also good.

[0022]

The plastisol of the present invention is excellent in viscosity stability and low temperature melting, and molded articles made from the plastisol have good volatility resistance and cold resistance.

Claims (1)

[Claims] 1. A plastisol containing vinyl chloride paste resin and di-2-propylheptyl phthalate as main components.